Controlled Assembly of Gold Nanostructures on a Solid Substrate via Imidazole Directed Hydrogen Bonding for High Performance Surface Enhance Raman Scattering Sensing of Hypochlorous Acid

Here, we report an efficient and facile method for constructing plasmonic gold nanostructures with controlled morphology on a Si wafer and its use as a surface enhanced Raman scattering (SERS) reporting system for specific detection of HClO. To achieve this substrate, the core gold nanoparticles (AuNPs, ∼100 nm) with a monolayer of 4-mercaptoimidazole (MI) ligands were covalently linked to a thiol-derived Si wafer (MI-AuNPs@SH-Si). Taking advantage of the intermolecular NH···N hydrogen bond (HB) provided by the neighboring imidazole moiety, multiple satellite AuNPs (∼12 nm) decorated with both MI and a Raman reporter are assembled around the core MI-AuNPs at pH 5.0. The uniform morphology of the AuNP-based nanostructures on the Si wafer offer a high density of hot spots with good SERS performance for detecting HClO. The fast oxidation of the imidazole moieties by HClO causes HB destruction and therefore separation of the satellite AuNPs from the core AuNPs, which gives rise to SERS signal damping of the chip that is employed for HClO analysis. This simple and cost-effective method is highly selective for HClO over common interferences and several reactive oxygen/nitrogen species, and enabled rapid analysis at concentrations as low as 1.2 μmol L^–1. The present approach is applied to analyze water and human serum samples with satisfactory results

Dynamic Monitoring of the Structural Evolution of Au@Pd under Electrochemistry

Core–shell nanocatalysts have shown superior catalytic activity than monometallic catalysts. However, these metastable materials are susceptible to structural changes during catalysis. Comprehending the evolution of surface sites and their stability under different reaction conditions is crucial for designing durable and highly active core–shell nanocatalysts. Herein, structural transformation of the atomic layer thickness of Pd shells on Au nanocubes in different electrolytes at various electrochemical windows was investigated by a combination of cyclic voltammetry (CV), surface-enhanced Raman spectroscopy (SERS) of adsorbed probe molecules, and elemental analysis. Pd sites are stable under basic and neutral conditions but experience severe structure evolution under acidic conditions. Pd atoms that are directly coordinated by Au atoms, upon oxidation at evaluated potential, transform into Pd ions via the reaction with H+ which would also be adsorbed on the Au sites. These Pd ions are easily coreduced with the formed Au ions into surface alloys in the backward CV scan. In contrast, Pd atoms in the thick Pd overlayer (>1 monolayer) are likely to dissolute into the electrolyte solution and leach. SERS revealed that the change of Pd sites primarily occurred at contiguous Pd sites and isolated Pd sites were relatively stable. This evolution mechanism provides new insight into the rational design of efficient and stable catalysts and is expected to promote further application of core–shell nanocatalysts

Fully Exposed Pd Ensembles on Ultrathin Co₃O₄ Nanosheets: A Reductive–Oxidative Dual-Active Catalyst for the Detoxification of Chlorophenol

The complete detoxification of hazardous organic pollutants is crucial for water treatment. However, this often requires the cooperation of multiple treatment processes catalyzed by different catalysts, leading to a complex water treatment infrastructure design and high operational costs. To address this challenge, we developed fully exposed palladium (Pd) ensemble (Pdn)-loaded ultrathin Co3O4 nanosheets (NSs) (Pdn/Co3O4 NSs) as a reductive–oxidative dual-active catalyst for the efficient detoxification of halogenated organic pollutants. During the treatment of simulated water contaminated by 4-chlorophenol (4-CP), a representative persistent organic pollutant, Pdn reactive centers rapidly hydrodechlorinate 4-CP into low-toxicity phenol with activity ≥10 times that of benchmark catalysts. The synergy between the Pd ensembles and oxygen vacancies further promotes the rapid and selective hydrogenation of phenol into cyclohexanone on Co3O4 NSs. Subsequently, cyclohexanone is oxidized by peroxymonosulfate (PMS) under Co3O4 activation. A cell assay-based toxicity study confirmed that stimulated polluted environmental water is fully detoxified after treatment with the designed Pdn/Co3O4 NSs catalyst. This study provides new insights into the rational design of Pd catalysts for the catalytic removal of persistent organic pollutants, particularly halogenated aromatics, paving the way for facile, low-cost, and highly efficient water treatment processes

Construction of a Degradation-Free DNA Conjugated Nanoprobe and Its Application in Rapid Field Screening for Sulfur Mustard

Sulfur mustard (SM) is a notorious blistering chemical warfare agent. Rapid field screening for trace SM is of vital significance for the detection of antiterrorism and timely treatment. Here, a visual assay for SM was constructed on the basis of its inhibition for the G-quadruplexes/hemin DNAzyme. Specifically, multiple guanine (G)-rich single stranded oligonucleotides (ssODN) named S1 (80% of G in the total bases), i.e., the precursor for G-quadruplex, which could oxide tetramethylbenzidine (TMB) to its green product, were conjugated on the nonfouling polymer brush grafted magnetic beads (MB@P­(C–H)). SM could specifically alkylate the N7 and O6 sites of G in the S1; thus, it failed to form the DNAzyme based signal reporter. It was demonstrated that the nonfouling P­(C–H) interface on the magnetic bead (MB) could protect the conjugated ssODN from nuclease degradation, thus ensuring its well sensing performance in complex samples. Under the optimized conditions, this method achieved good sensitivity and selectivity with a limit of detection (LOD) as low as 0.26 μmol L–1, and the recoveries ranging from 86% to 117% were obtained for different SM spiked real samples. Above all, this method combining low cost and ready operation could be suited for rapid field SM screening in a wide range of environmental matrices